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Ukukhiqiza okungeziwe kushintsha indlela abacwaningi nosozimboni abaklama futhi benze ngayo izinto zamakhemikhali ukuze zihlangabezane nezidingo zabo ezithile. Kulo msebenzi, sibika isibonelo sokuqala se-reactor egelezayo eyakhiwe yisu le-solid-state metal sheet lamination technique I-Ultrasonic Additive Manufacturing (UAM) enezingxenye ze-catalytic ezididiyelwe kanye nezici zokuzwa. Akukhona nje kuphela ukuthi ubuchwepheshe be-UAM bunqoba imingcele eminingi ehlobene namakhemikhali anjalo manje, futhi kwandisa amandla anjalo amakhemikhali anamandla. uchungechunge lwezinhlanganisela ezibalulekile ngokwebhayololi eziyi-1,4-disubstituted 1,2,3-triazole zenziwe ngempumelelo futhi zalungiswa nge-Cu-mediated Huisgen 1,3-dipolar cycloaddition reaction kusetshenziswa ukusetha kwekhemistri ye-UAM.
Ngenxa yezinzuzo zayo eziphawulekayo ngaphezu komlingani wayo omningi, i-flow chemistry iyinkambu ebalulekile futhi ekhulayo kuzo zombili izilungiselelo zezemfundo nezimboni ngenxa yekhono layo lokwandisa ukukhetha nokusebenza kahle kwe-chemical synthesis.Lokhu kudlulela kusukela ekubunjweni kwe-organic molecule1 kuya kumakhemikhali emithi2,3 kanye nemikhiqizo yemvelo4,5,6. Ukusabela okungaphezulu kuka-50% ezimbonini ezinhle zamakhemikhali nezemithi kungazuza ekusebenziseni ukucubungula kokugeleza okuqhubekayo7.
Eminyakeni yamuva nje, kube nomkhuba okhulayo wamaqembu afuna ukufaka esikhundleni se-glassware yendabuko noma imishini yamakhemikhali agelezayo nge-customizable additive manufacturing (AM) chemistry "reaction vessels"8.Idizayini ephindaphindayo, ukukhiqiza okusheshayo, kanye namakhono angu-3-dimensional (3D) alawa maqhinga anenzuzo kulabo abafisa ukwenza ngokwezifiso amadivayisi abo kusethi ethile yokusabela, idethi, ukusetshenziswa okukhethekile okugxile ekugxileni okukhethekile. amasu okuphrinta e-3D asekelwe ku-polymer njenge-stereolithography (SL)9,10,11, i-fused deposition modeling (FDM)8,12,13,14 kanye nokuphrinta kwe-inkjet 7, 15, 16. Ukuntuleka kokuqina kanye nekhono lamathuluzi anjalo okwenza uhla olubanzi lokusabela kwamakhemikhali/ukuhlaziywa kwesici esibanzi esingu-18201, ukuqaliswa okubanzi kwe-18207, 9 ka-AM kulo mkhakha17, 18, 19, 20 .
Ngenxa yokwanda kokusetshenziswa kwekhemikhali yokugeleza kanye nezakhiwo ezithandekayo ezihlotshaniswa ne-AM, kunesidingo sokuhlola amasu athuthuke kakhulu avumela abasebenzisi ukuthi bakhe imikhumbi yokusabela kokugeleza ngamandla athuthukisiwe amakhemikhali nawokuhlaziya.Lawa masu kufanele avumele abasebenzisi ukuthi bakhethe ohlwini lwezinto eziqinile noma ezisebenzayo ezikwazi ukuphatha izimo ezihlukahlukene zokusabela, kuyilapho kusiza izinhlobo ezihlukahlukene zokulawula ukusabela okuvela kudivayisi nokulawula okuphumayo.
Inqubo eyodwa yokukhiqiza i-additive enamandla okuthuthukisa ama-reactors amakhemikhali angokwezifiso i-Ultrasonic Additive Manufacturing (UAM) .Le nqubo ye-solid-state sheet lamination isebenzisa ama-oscillations e-ultrasonic kuma-foil ensimbi amancane ukuze ahlanganise ndawonye ungqimba ngongqimba olunokushisa okuncane kakhulu kanye nezinga eliphezulu lokugeleza kwe-plastic 21 , 22 , 23 .Ngokungafani nezinye izinto ezihlanganisiwe ze-AM ezihlanganisiwe, ngokungafani nezinye i-AM eyaziwayo, i-subtechnics eyaziwayo ngokuqondile, i-AM eyaziwa kakhulu. njengenqubo yokukhiqiza eyingxube, lapho i-in-situ periodic computer numberal control (CNC) milling noma laser machining ichaza ukuma kwenetha kongqimba lwempahla eboshiwe 24, 25.Lokhu kusho ukuthi umsebenzisi akakhawulelwe ngezinkinga ezihambisana nokukhipha insalela yokwakha eluhlaza eziteshini ezincane eziwuketshezi, okuvamise ukuba njalo ngempushana noketshezi oluwuketshezi kunganwetshwa amasistimu we-AM28 atholakalayo,27. ibhondi inhlanganisela yezinto ezifanayo ezishisayo nezingafanani esinyathelweni esisodwa senqubo.Ukukhethwa kwenhlanganisela yezinto ezibonakalayo ngale kwenqubo yokuncibilika kusho ukuthi izimfuno zemishini nezamakhemikhali zezinhlelo ezithile zokusebenza zingahlangatshezwana kangcono.Ngaphezu kokuhlanganisa isimo esiqinile, enye into ehlangatshezwane nayo ngesikhathi sokuhlanganiswa kwe-ultrasonic ukugeleza okuphezulu kwezinto zepulasitiki emazingeni okushisa aphansi kakhulu29,30,31,31,32,3AM. izendlalelo ezingenakonakala.Izinzwa ezishumekiwe ze-UAM zingasiza ukulethwa kolwazi lwesikhathi sangempela kusuka kudivayisi kuya kumsebenzisi ngezibalo ezihlanganisiwe.
Umsebenzi wangaphambili wababhali32 ubonise ikhono lenqubo ye-UAM yokudala izakhiwo ze-3D microfluidic metallic ezinamandla okuzwa okuhlanganisiwe.Lena iyithuluzi lokuqapha kuphela.Leli phepha lethula isibonelo sokuqala se-microfluidic chemical reactor eyakhiwe yi-UAM; idivayisi esebenzayo engaqapheli nje kuphela kodwa futhi idonsa ukuhlanganiswa kwamakhemikhali ngokusebenzisa izinto ezikhuthazayo ezihlanganisiwe ngokwesakhiwo.Idivayisi ihlanganisa izinzuzo ezimbalwa ezihambisana nobuchwepheshe be-UAM ekukhiqizeni idivayisi yamakhemikhali ye-3D, njengalezi: ikhono lokuguqula imiklamo egcwele ye-3D ngokuqondile kusuka kumamodeli we-computer-aid design (CAD) ibe yimikhiqizo; ukwakhiwa kwezinto eziningi ukuze kuhlanganiswe izinga eliphezulu le-thermal conductivity kanye nezinto ze-catalytic; kanye nokushumeka izinzwa ezishisayo ngokuqondile phakathi kokugeleza kwe-reagent ukuze kugadwe izinga lokushisa elinembile nokulawula.Ukubonisa ukusebenza kwe-reactor, umtapo wolwazi wezingxube ezibalulekile ze-1,4-disubstituted 1,2,3-triazole obalulekile ngokwemithi wahlanganiswa yi-Huisgen 1,3-dipolar ye-copper-catalyzed. ukuklama kungavula amathuba amasha kanye namathuba ekhemistri ngocwaningo lwemikhakha eminingi.
Zonke izincibilikisi nama-reagents athengwe kwa-Sigma-Aldrich, Alfa Aesar, TCI noma i-Fischer Scientific futhi asetshenziswa ngaphandle kokuhlanzwa kwangaphambili.1H kanye ne-13C NMR spectra erekhodwe ku-400 MHz kanye no-100 MHz, ngokulandelana, atholwe kusetshenziswa i-JEOL ECS-400 400 MHz 400 MHz 400 MHz noma i-Bruu 400 MHz spectra. i-spectrometer ne-CDCl3 noma (CD3)2SO njenge-solvent.Konke ukusabela kwenziwa kusetshenziswa iplatifomu yekhemistri egelezayo ye-Uniqsis FlowSyn.
I-UAM yasetshenziswa ukwenza wonke amadivaysi kulolu cwaningo.Ubuchwepheshe basungulwa ngo-1999, futhi imininingwane yabo yobuchwepheshe, imingcele yokusebenza kanye nentuthuko kusukela yasungulwa ingacwaningwa ngezinto ezishicilelwe ezilandelayo34,35,36,37.Idivayisi (Umfanekiso 1) yasetshenziswa kusetshenziswa amandla aphezulu kakhulu, 9kW SonicLayer UAM 4000 uhlelo lwe-USA, i-OHbri ekhethiwe ye-USA, i-OHbri yesistimu ye-USA. ukwakhiwa kwedivayisi yokugeleza bekuyi-Cu-110 kanye ne-Al 6061.Cu-110 inokuqukethwe kwethusi okuphezulu (ubuncane obungu-99.9% bethusi), okuyenza ibe ikhandidethi elihle lokusabela okwenziwe ngethusi, futhi ngenxa yalokho isetshenziswa “njengesendlalelo esisebenzayo ngaphakathi kwe-microreactor. isimo se-annealed esihlanganiswe ne-Cu-110 layer i-Al 6061 O iyinto ekhonjiswe ukuthi ihambisana kakhulu nezinqubo ze-UAM38, 39, 40, 41 futhi ihloliwe futhi yatholakala izinzile ngokwekhemikhali nama-reagents asetshenziswe kulo msebenzi. 38,42 Lezi zisetshenziswa zibalwe kuThebula 1 ngezansi.
Izigaba zokwenziwa kwe-reactor (1) I-Al 6061 substrate (2) Ukwenziwa kwesiteshi esingaphansi esisethwe ku-foil yethusi (3) Ukushumeka kwama-thermocouples phakathi kwezendlalelo (4) Ishaneli ephezulu (5) I-Inlet ne-outlet (6) i-Monolithic reactor.
Ifilosofi yokuklama yendlela yoketshezi iwukusebenzisa indlela ehlanganisiwe ukuze kwandiswe ibanga elihamba uketshezi ngaphakathi kwe-chip, kuyilapho ugcina i-chip ikusayizi olawulekayo.Lokhu kukhuphuka kwebanga kuyadingeka ukuze kukhushulwe isikhathi sokusebenzisana se-catalyst/reagent futhi kunikeze izinzuzo ezinhle kakhulu zomkhiqizo.Ama-chips asebenzisa ukugoba okungu-90° ekugcineni kwendlela eqondile ukuze angenise ngaphakathi kwendawo enyakazayo yedivayisi4 uketshezi oluxubekile4 (i-catalyst).Ukuqhubeka nokwandisa ukuxuba okungafinyelelwa, umklamo we-reactor uhlanganisa ama-reagent inlets amabili ahlanganiswe ku-Y-junction ngaphambi kokungena esigabeni sokuxuba inyoka.I-inlet yesithathu, enqamula umfudlana phakathi nendawo lapho ihlala khona, ifakiwe ekwakhiweni kwe-multistep reaction syntheses yesikhathi esizayo.
Zonke iziteshi zinephrofayela eyisikwele (awekho ama-engeli asalungiswa), umphumela wokugaya ngezikhathi ezithile kwe-CNC okusetshenziselwa ukudala i-geometry yesiteshi. Ubukhulu besiteshi bukhethwa ukuze kuqinisekiswe ukuphuma kwevolumu ephezulu (ye-microreactor), kuyilapho buncane ngokwanele ukuze kube lula ukusebenzisana kwendawo (ama-catalyst) kuketshezi oluningi oluqukethwe. µm x 750 µm kanye nesamba sevolumu ye-reactor bekungu-1 ml.Isixhumi esihlanganisiwe (1/4″—28 intambo ye-UNF) sifakiwe ekwakhiweni kokuvumela ukuhlobana okulula kwedivayisi ngempahla yekhemistri egeleza ngokwentengiso. Usayizi wesiteshi unqunyelwe ubukhulu bezinto ze-foil, izakhiwo zayo zemishini, kanye nemingcele yokubopha esetshenziswa nama-ultrasonics. Ngobubanzi obuthile bento enikeziwe, okokusebenza "kuzocwila" kusiteshi esidaliwe. Okwamanje ayikho imodeli ethile yalesi sibalo, ngakho ububanzi besiteshi esiphezulu sento enikeziwe kanye nomklamo bunqunywa ngokuhlola; kulokhu, ububanzi be-750 μm ngeke bubangele i-sag.
Ukuma (isikwele) sesiteshi kunqunywa ngokusebenzisa i-square cutter.Umumo nobukhulu beziteshi kungashintshwa ngemishini ye-CNC kusetshenziswa amathuluzi okusika ahlukene ukuze kutholwe amazinga okugeleza ahlukene kanye nezici.Isibonelo sokwenza isiteshi somumo ogobile usebenzisa ithuluzi le-125 μm singatholakala emsebenzini we-Monaghan45.Lapho ungqimba lwe-foil lubekwe phezu kwepulani le-foil lizoba nemfashini phezu kwepulani eliyisicaba. (isikwele) finish.Kulo msebenzi, ukuze kugcinwe ukulinganisa kwesiteshi, kusetshenziswe uhlaka lwesikwele.
Ngesikhathi sokumisa okwesikhashana lapho kukhiqizwa, ama-thermocouple amazinga okushisa (Uhlobo K) ashumekwe ngokuqondile ngaphakathi kwedivayisi phakathi kwamaqembu amashaneli aphezulu naphansi (Umfanekiso 1 - Isiteji sesi-3). Lawa ma-thermocouples angakwazi ukuqapha izinguquko zokushisa ukusuka ku-−200 kuya ku-1350 °C.
Inqubo yokubeka insimbi yenziwa uphondo lwe-UAM lisebenzisa i-foil yensimbi engu-25.4 mm ububanzi, i-micron eyi-150 yensimbi. ubukhulu bezinto ezifakiwe zikhulu kunomkhiqizo wokugcina njengoba inqubo yokukhipha ikhiqiza isimo sokugcina senetha.Umshini we-CNC usetshenziselwa umshini ama-contours angaphandle nangaphakathi wemishini, okuholela ekuqedeni okungaphezulu kwemishini namashaneli alingana nethuluzi elikhethiwe kanye nemingcele yenqubo ye-CNC (cishe i-1.6 μm Ra kulesi sibonelo) . qinisekisa ukunemba kwe-dimensional kugcinwa futhi ingxenye eqediwe izohlangabezana namazinga okunemba wokuqeda ukugaya kwe-CNC.Ububanzi besiteshi obusetshenziselwa le divayisi buncane ngokwanele ukuze kuqinisekiswe ukuthi impahla ye-foil "ayicwili" esiteshini samanzi, ngakho-ke isiteshi sigcina isikwele se-cross-section.Izikhala ezingenzeka ku-foil material kanye nemingcele yenqubo ye-UAM yanqunywa ngokuhlola nguzakwethu wokukhiqiza, i-USA Fabrisonic).
Ucwaningo lubonise ukuthi ukusabalalisa okuncane kwe-elementi kwenzeka ku-UAM bonding interface 46, 47 ngaphandle kokwelashwa okushisayo okwengeziwe, ngakho-ke kumadivayisi akulo msebenzi, ungqimba lwe-Cu-110 luhlala luhlukile kungqimba lwe-Al 6061 futhi lushintsha kungazelelwe.
Faka isilawuli se-back pressure (BPR) esilinganiselwe ngaphambili esingu-250 (1724 kPa) ekuphumeni kwereactor bese umpompa amanzi ngereactor ngesilinganiso esingu-0.1 kuya ku-1 mL min-1. Ukucindezela kwereactor kwaqashwa kusetshenziswa inzwa ye-FlowSyn eyakhelwe ngaphakathi yesistimu yokucindezela ukuze kuqinisekiswe ukuthi isistimu yayikwazi ukugcina noma iyiphi i-reactor egelezayo engaguquguquki yonkana ingcindezi egelezayo ye-reactor. umehluko phakathi kwama-thermocouples ashumekwe ngaphakathi kwe-reactor nalawo ashumekwe ngaphakathi kwepuleti lokushisa le-FlowSyn chip.Lokhu kufinyelelwa ngokushintsha izinga lokushisa le-hotplate elihlelekayo phakathi kuka-100 no-150 °C ekunyukeni okungu-25 °C nokuqaphela noma yimuphi umehluko phakathi kwamazinga okushisa ahleliwe narekhodiwe.Lokhu kufinyelelwe kusetshenziswa i-datach, UK8Tech, i-UK datach, i-Cambridge ehambisana nesofthiwe ye-PicoLog.
Izimo zokusabela kwe-cycloaddition ze-phenylacetylene ne-iodoethane zathuthukiswa (I-Scheme 1- Cycloaddition of phenylacetylene kanye ne-iodoethane Scheme 1- Cycloaddition of phenylacetylene and iodoethane). Lokhu kulungiselelwa kwenziwa ngokuklanywa okuphelele kwe-factory yokuhlola (i-DOE) njengendlela yokuhlola izinga lokushisa, kusetshenziswa indlela yokuhlola eguquguqukayo (i-DOE) isilinganiso se-alkyne:azide ku-1:2.
Izixazululo ezihlukene ze-sodium azide (0.25 M, 4:1 DMF:H2O), iodoethane (0.25 M, DMF), ne-phenylacetylene (0.125 M, DMF) zalungiswa.I-aliquot engu-1.5 mL yesixazululo ngasinye yaxutshwa futhi yampontshwa nge-reactor ngezinga lokugeleza elifiswayo kanye nezinga lokushisa njengoba imodeli ye-pezole yokusabela ithathwe endaweni yomkhiqizo we-pezole yathathwa. i-phenylacetylene yokuqala impahla futhi inqunywa ukusebenza okuphezulu kwe-liquid chromatography (HPLC).Ngokuvumelana kokuhlaziywa, konke ukusabela kwathathwa isampula ngemva nje kokuba ingxube yokusabela ishiye i-reactor.Ububanzi bepharamitha obukhethelwe ukulungiselelwa buboniswa kuThebula lesi-2.
Wonke amasampuli ahlaziywa kusetshenziswa isistimu ye-Chromaster HPLC (VWR, PA, USA) ehlanganisa iphampu ye-quaternary, i-oven yekholomu, umtshina we-UV oguquguqukayo we-wavelength kanye ne-autosampler.Ikholomu ibiyi-Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 mm ngosayizi, 5 µm usayizi wezinhlayiyana, i-5 µm yalungiswa ngosayizi we-5 µm. I-isocratic 50:50 methanol:amanzi ngesilinganiso sokugeleza esingu-1.5 mL.min-1.Ivolumu yomjovo ibingu-5 µL futhi ubude bendawo yomtshina bebungu-254 nm. Indawo ephakeme engu-% yesampula ye-DOE ibalwe kusukela ezindaweni eziphakeme ze-alkyne ezisele kanye ne-triazole yemikhiqizo ehambisanayo yokuqala.
Ukuhlanganisa okukhiphayo kokuhlaziywa kwe-reactor kusofthiwe ye-MODDE DOE (i-Umetrics, i-Malmö, i-Sweden) kuvumele ukuhlaziya okuphelele kwamathrendi wemiphumela kanye nokunqunywa kwezimo ezilungile zokusabela zale cycloaddition.Ukusebenzisa isilungiseleli esakhelwe ngaphakathi nokukhetha yonke imibandela yemodeli ebalulekile kuveza isethi yezimo zokusabela eziklanyelwe ukukhulisa indawo ephakeme yomkhiqizo ngenkathi kunciphisa indawo ephakemeyo yokuqala yomkhiqizo ngenkathi kunciphisa inani eliphakeme lendawo yokuqala.
Ukufakwa kwe-oxidation yethusi engaphezulu ngaphakathi kwegumbi le-catalytic reaction kwafinyelelwa kusetshenziswa isixazululo se-hydrogen peroxide (36%) egeleza egumbini lokusabela (izinga lokugeleza = 0.4 mL min-1, isikhathi sokuhlala = 2.5 min) ngaphambi kokuhlanganiswa komtapo wezincwadi we-triazole ngamunye.
Lapho isethi yemibandela efanele ibonakalisiwe, isetshenziswe kuhlu lwe-acetylene kanye ne-haloalkane derivatives ukuvumela ukuhlanganiswa kokuhlanganiswa komtapo omncane, ngaleyo ndlela kusungulwe ikhono lokusebenzisa lezi zimo kuhlu olubanzi lwama-reagents angaba khona (Umfanekiso 1) .2).
Lungiselela izixazululo ezihlukene ze-sodium azide (0.25 M, 4:1 DMF:H2O), ama-haloalkanes (0.25 M, DMF) nama-alkynes (0.125 M, DMF). Ama-aliquots angu-3 mL esixazululo ngasinye axutshwe futhi ampontshwa ngereactor engu-75 µL.min-1 kanye no-150 °C futhi yahlanganiswa ibe yingqikithi ye-vial engu-10 °C. I-ethyl acetate.Isixazululo sesampula sagezwa nge-3 × 10 mL yamanzi.Izingqimba ezinamanzi zahlanganiswa futhi zakhishwa nge-10 mL ye-ethyl acetate; izingqimba zezinto eziphilayo zabe sezihlanganiswa, zagezwa nge-3 x 10 mL ye-brine, zomiswa phezu kwe-MgSO4 futhi zihlungiwe, bese i-solvent ikhishwa ku-vacuo.Amasampuli ahlanzwa ngekholomu ye-chromatography ku-silica gel kusetshenziswa i-ethyl acetate ngaphambi kokuhlaziywa ngenhlanganisela ye-HPLC, 1H NMR, 13C HR-spection ye-HR (i-high resolution mass NMR).
Wonke ama-spectra atholwe kusetshenziswa i-Thermofischer precision Orbitrap mass spectrometer ene-ESI njengomthombo we-ionization.Wonke amasampuli alungiswa kusetshenziswa i-acetonitrile njenge-solvent.
Ukuhlaziywa kwe-TLC kwenziwa kumapuleti e-silica ane-aluminium-backed.
Wonke amasampula ahlaziywa kusetshenziswa isistimu ye-VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) efakwe i-autosampler, ikholomu yephampu ye-oven kanambambili kanye nomtshina we-wavelength eyodwa.Ikholomu esetshenzisiwe kwakuyi-ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Ltd,Scotland Aberones).
Imijovo (5 µL) yenziwe ngokuqondile kusukela kungxube yokusabela okungcolile okuhlanjululiwe (i-1:10 dilution) futhi yahlaziywa ngamanzi:i-methanol (50:50 noma 70:30), ngaphandle kwamasampuli athile kusetshenziswa isistimu ye-solvent engu-70:30 (echazwa njengenombolo yenkanyezi) ngesilinganiso sokugeleza esingu-1.5 mL ikholomu igcinwe ku-4 ° ikholomu noma i-wangth. 254 nm.
Indawo ephakeme engu-% yesampula ibalwa kusukela endaweni ephakeme kakhulu ye-alkyne esele, umkhiqizo we-triazole kuphela, futhi umjovo wento yokuqala uvumele ukukhonjwa kweziqongo ezifanele.
Wonke amasampula ahlaziywa kusetshenziswa i-Thermo iCAP 6000 ICP-OES.Wonke amazinga okulinganisa alungiswa kusetshenziswa isisombululo esijwayelekile esingu-1000 ppm Cu ku-2% nitric acid (SPEX Certi Prep).Wonke amazinga alungiswe ngesixazululo esingu-5% DMF no-2% HNO3, futhi wonke amasampula ahlanjululwe isixazululo se-DMF esiphindwe ku-20-H3 kusixazululo esingu-20-H3.
I-UAM isebenzisa i-ultrasonic metal welding njengendlela yokubopha insimbi yensimbi esetshenziselwa ukwakha i-asembly yokugcina.I-ultrasonic metal welding isebenzisa ithuluzi lensimbi elidlidlizayo (elibizwa ngokuthi uphondo noma uphondo lwe-ultrasonic) ukuze ifake ingcindezi kungqimba lwe-foil / ungqimba oluhlanganisiwe ngaphambili oluzohlanganiswa ngenkathi ludlidliza. ukubopha yonke indawo.Lapho ukucindezela nokudlidliza kusetshenziswa, ama-oxide ebusweni bezinto ezibonakalayo angaqhekeka.Ukucindezela okuqhubekayo nokudlidliza kungabangela ukuba ama-asperities wento adilike 36 .Ukuxhumana okuseduze nokushisa okudalwe endaweni kanye nokucindezela bese kuholela ekubopheni isimo esiqinile ezindaweni ezibonakalayo; kungasiza futhi ukunamathela ngokusebenzisa izinguquko zamandla angaphezulu48.Imvelo yendlela yokubopha inqoba izinkinga eziningi ezihambisana nokushisa okuguquguqukayo kokuncibilika kanye nokushisa okuphezulu ngemva kwemiphumela okukhulunywe ngayo kwamanye amasu okukhiqiza okungeziwe.Lokhu kuvumela ukubopha okuqondile (okungukuthi, ngaphandle kokuguqulwa kwendawo, ama-fillers noma ama-adhesives) wezingqimba eziningi zezinto ezihlukahlukene zibe isakhiwo esisodwa esihlanganisiwe.
Isici sesibili esivumayo se-UAM yizinga eliphakeme lokugeleza kwepulasitiki elibhekwa ezintweni zensimbi, ngisho namazinga okushisa aphansi, okungukuthi ngaphansi kwendawo yokuncibilika yezinto zensimbi.Inhlanganisela ye-oscillation ye-ultrasonic kanye nokucindezela kubangela amazinga aphezulu okufuduka komngcele wokusanhlamvu wendawo kanye nokuvuselelwa kabusha ngaphandle kokukhuphuka okukhulu kwezinga lokushisa okuvame ukuhlotshaniswa nezinto eziningi. ucwecwe lwensimbi, ungqimba ngongqimba.Izinto ezinjengemicu ye-optical 49, i-reinforcement 46, i-electronics 50, kanye nama-thermocouples (lo msebenzi) wonke ashumekwe ngempumelelo ezakhiweni ze-UAM ukuze kwakheke imihlangano eyinhlanganisela esebenzayo nengenzi lutho.
Kulo msebenzi, kokubili okuhlukene okuhlanganisayo okuhlanganayo kanye namathuba okuxhumana e-UAM kusetshenziswe ukwakha i-microreactor yokugcina ebambe iqhaza yokuqapha izinga lokushisa.
Uma kuqhathaniswa ne-palladium (Pd) nezinye izinto ezisetshenziswa ngokuvamile zensimbi, i-Cu catalysis inezinzuzo ezimbalwa: (i) Ngokomnotho, i-Cu ibiza kancane kunezinye izinsimbi eziningi ezisetshenziswa ku-catalysis ngakho-ke iyindlela ekhangayo embonini yokucutshungulwa kwamakhemikhali (ii) Ububanzi be-Cu-catalyzed cross-coupling reactions buyanda futhi bubonakala buhambisana kancane ne-Pd51,3o (2) Ukusabela kwe-Cu-catalyzed kusebenza kahle uma ingekho eminye imigqa, Lawa ma-ligand avame ukuba lula ngesakhiwo futhi angabizi uma efunwa, kuyilapho lawo asetshenziswa ku-Pd chemistry ngokuvamile ayinkimbinkimbi, ayabiza, futhi azwela emoyeni (iv) Cu, eyaziwa kakhulu ngekhono lawo lokuhlanganisa ama-alkynes ekuhlanganiseni, Ngokwesibonelo, i-bimetallic-catalyzedcling-cocatalyzedupling ikhemistri) (v) I-Cu iyakwazi futhi ukugqugquzela ukuvuthwa kwama-nucleophiles amaningana ekuphenduleni kohlobo lwe-Ullmann.
Izibonelo ze-heterogenization yazo zonke lezi zimo zisanda kuboniswa phambi kwe-Cu(0) .Lokhu kubangelwa kakhulu imboni yezemithi kanye nokugxila okukhulayo ekubuyiseleni i-metal catalyst kanye nokusetshenziswa kabusha55,56.
Iqalwe ngu-Huisgen ngeminyaka yawo-1960s57, ukusabela kwe-1,3-dipolar cycloaddition phakathi kwe-acetylene ne-azide kuya ku-1,2,3-triazole kuthathwa njengokusabela kokubonisa okuhambisanayo. Imiphumela engu-1,2,3 ye-triazole ithakazelisa ngokukhethekile njengomkhakha wokuthola imithi ehlukahlukene emkhakheni we-pharmacophore ama-ejenti okwelapha 58.
Lokhu kusabela kwaphinde kwagxila lapho u-Sharpless nabanye bethula umqondo wokuthi "chofoza i-chemistry"59.Igama elithi "chofoza ikhemistri" lisetshenziselwa ukuchaza isethi eqinile, ethembekile futhi ekhethiwe yokusabela kokuhlanganiswa okusheshayo kwamakhompiyutha amasha nemitapo yolwazi ehlanganisiwe nge-heteroatom linkage (CXC)60 Ukwenziwa kwalezi zimo zokusabela kubangelwa ukungezwani kwamanzi okuhlobene, ukusabela okuphezulu kwamanzi okuhambisanayo, ukusabela kwawo okuhlobene komoya-mpilo, ukusabela kwamanzi okuhlobene nokuphikisana nomkhiqizo wawo, ukusabela kwe-oksijini okuhlobene nomkhiqizo, ukusabela okuhlobene komoya-mpilo. ukuhlukana kulula61.
I-classical Huisgen 1,3-dipole cycloaddition ayiyona ingxenye yesigaba "sekhemistri yokuchofoza".Kodwa-ke, i-Medal ne-Sharpless ibonise ukuthi lo mcimbi wokuhlanganisa we-azide-alkyne udlula u-107 kuya ku-108 phambi kwe-Cu(I) uma kuqhathaniswa ne-uncatalyzed 1,3-dipolar 3-dipolar acceledi 62 acceledi reaction ephawulekayo. ayidingi ukuvikela amaqembu noma izimo zokusabela ezinzima kanye nemikhiqizo eseduze nokuguqulwa okuphelele nokukhetha ku-1,4-disubstituted 1,2,3-triazoles (anti- 1,2,3-triazole) esikalini sesikhathi (Umfanekiso 3).
Imiphumela ye-Isometric ye-Huisgen cycloadditions evamile ne-copper-catalyzed.Cu(I)-catalyzed Huisgen cycloadditions ikhiqiza kuphela i-1,4-disubstituted 1,2,3-triazoles, kanti ama-cycloadditions e-Huisgen enziwe nge-thermal ngokuvamile akhiqiza ingxube engu-1,51-atrizole ama-stereoisomers we-azoles.
Amaphrothokholi amaningi ahilela ukuncishiswa kwemithombo ezinzile ye-Cu(II), njengokuncishiswa kwezinhlobo ze-CuSO4 noma i-Cu(II)/Cu(0) ukuhlanganiswa nosawoti we-sodium.Uma kuqhathaniswa nokunye ukusabela okwenziwe ngensimbi, ukusetshenziswa kwe-Cu(I) kunezinzuzo ezinkulu zokungabizi futhi kulula ukuphatha.
Izifundo zokulebula ze-Kinetic ne-isotopic zika-Worrell et al. 65 ibonise ukuthi, esimweni sama-alkynes esibulalayo, izinto ezilinganayo ezimbili zethusi ziyabandakanyeka ekwenzeni kusebenze ukusebenza kabusha kwe-molecule ngayinye ukuya ku-azide.Indlela ehlongozwayo iqhubeka ngendandatho yethusi enamalungu ayisithupha eyakhiwe ngokuxhumanisa kwe-azide ku-σ-bond acetylide yethusi enethusi eliboshwe ngu-π njengomnikelo oqinile we-copper oqinile. ukuncipha kwendandatho, okulandelwa ukubola kweproton ukuze kuhlinzekwe ngemikhiqizo ye-triazole nokuvala umjikelezo we-catalytic.
Nakuba izinzuzo zamadivayisi we-flow chemistry zibhalwe kahle, kube nesifiso sokuhlanganisa amathuluzi okuhlaziya kulezi zinhlelo ze-in-line, in-situ, ukuqapha inqubo66,67.UAM ibonakale iyindlela efanelekile yokuklama nokukhiqiza ama-flow reactors e-3D ayinkimbinkimbi kakhulu enziwe ngezinto ezisebenzayo, ezisebenza ngokushisa okushisayo ezinezinzwa ze-4 ezishumekiwe ngokuqondile ().
I-Aluminium-copper flow reactor eyakhiwe ukukhiqizwa kwe-ultrasonic additive (UAM) enesakhiwo sesiteshi sangaphakathi esiyinkimbinkimbi, ama-thermocouples ashumekiwe kanye ne-catalytic reaction chamber.
Ukuqinisekisa ukuthi ama-reactors akhelwe ukusabela kwe-organic esizayo, izincibilikisi zidinga ukushisisa ngokuphephile ngaphezu kwendawo yokubilisa; zivivinywa ukucindezela nokushisa.Ukuhlolwa kwengcindezi kubonise ukuthi uhlelo lugcina ukucindezela okuzinzile nokuqhubekayo ngisho nokucindezela kwesistimu okwenyuka (1.7 MPa) .Ukuhlolwa kwe-hydrostatic kwenziwa ekamelweni lokushisa kusetshenziswa i-H2O njengoketshezi.
Ukuxhuma i-thermocouple eshumekiwe (Umfanekiso 1) kumshini wokufaka idatha wezinga lokushisa kubonise ukuthi i-thermocouple ibipholile ngo-6 °C (± 1 °C) kunezinga lokushisa elihleliwe ohlelweni lwe-FlowSyn. Ngokuvamile, ukunyuka kwezinga lokushisa ngo-10 °C kubangela ukuphindaphindeka kwezinga lokusabela, ngakho-ke umehluko wezinga lokushisa wamadigri ambalwa nje ngenxa yomehluko wokushintsha izinga lokushisa ngenxa yokusabela komzimba. high diffusivity ezishisayo izinto ezisetshenziswa inqubo yokukhiqiza.Lokhu drift thermal kuyavumelana futhi ngakho-ke kungabalwa ekusethweni kwemishini ukuqinisekisa amazinga okushisa anembile afinyelelwa futhi kukalwa ngesikhathi reaction.Ngakho-ke, leli thuluzi lokuqapha ku-inthanethi lisiza ukulawula okuqinile kwezinga lokushisa lokusabela futhi lisiza ukuthuthukiswa kwenqubo enembe kakhudlwana kanye nokuthuthukiswa kwezimo ezifanele.Lezi zinzwa zikwazi ukukhomba ukusabela okukhulu kwe-reactional futhi kungasetshenziswa ukuvimbela ukusabela okukhulu.
I-reactor eyethulwe kulo msebenzi iyisibonelo sokuqala sokusetshenziswa kobuchwepheshe be-UAM ekwakhiweni kwama-reactors amakhemikhali futhi ibhekana nemikhawulo eminingana emikhulu okwamanje ehlotshaniswa nokuphrinta kwe-AM/3D yalawa madivayisi, njengalokhu: (i) ukunqoba izinkinga ezibikiwe ezihlobene nokucubungula ithusi noma i-aluminium alloy processing (ii) ukulungiswa kwesiteshi okuthuthukisiwe kwangaphakathi uma kuqhathaniswa ne-powder bed fusion (PBF) noma amasu okugeleza kwe-laser2 okukhethayo (SLM) amasu okugeleza kwe-laser2 kanye nezindlela zokugeleza ze-laser25, i-SLM yokugeleza kwe-laser5 kanye nezici zokugeleza ze-SLM2. ukuthungwa kwendawo emaholoholo26 (iii) Ukuncipha kwezinga lokushisa lokucubungula, okwenza kube lula ukuhlangana okuqondile kwezinzwa, okungenakwenzeka kubuchwepheshe bombhede oyimpushana, (v) kwehlula izici zemishini ezimbi kanye nokuzwela kwezingxenye zezingxenye ezisekelwe ku-polymer ezinhlobonhlobo zezincibilikisi eziphilayo ezivamile17,19.
Ukusebenza kwe-reactor kuboniswe uchungechunge lwe-alkyne azide cycloaddition reactions yethusi-catalyzed ngaphansi kwezimo zokugeleza okuqhubekayo (Fig. 2) .I-reactor yethusi ephrintiwe nge-ultrasonic echazwe ku-Figure 4 ihlanganiswe nohlelo lokugeleza kwezentengiselwano futhi yasetshenziselwa ukuhlanganisa ama-azides omtapo wezincwadi ezihlukahlukene ze-1,4-disubstituted i-3-athol-azoled ye-1,4-disubstituted i-athol-azoled yokulawula izinga lokushisa kwe-1,4-disubstituted 1,4-disubstituted 3-tricealed-azoled reaction-control, kanye namaqembu e-alkyl ama-halides phambi kwe-sodium chloride (Umfanekiso 3) .Ukusetshenziswa kwendlela yokugeleza okuqhubekayo kunciphisa ukukhathazeka kokuphepha okungavela ezinkambisweni ze-batch, njengoba lokhu kusabela kukhiqiza ama-aside intermediates asebenzayo kakhulu futhi ayingozi [317], [318]. I-Cycloaddition ye-phenylacetylene ne-iodoethane) (bheka Umfanekiso 5).
(Phezulu kwesokunxele) Isikimu sokusetha okusetshenziselwa ukufaka i-reactor ye-3DP ohlelweni lokugeleza (phezulu kwesokudla) esitholwe kuhlelo olulungiselelwe (phansi) lohlelo lwe-Huisgen cycloaddition 57 phakathi kwe-phenylacetylene ne-iodoethane ukuze kuthuthukiswe futhi kuboniswe izinga lokuguqulwa kwamapharamitha athuthukisiwe.
Ngokulawula isikhathi sokuhlala sama-reagents engxenyeni ye-catalytic ye-reactor kanye nokuqapha ngokucophelela izinga lokushisa lokusabela nge-thermocouple probe edidiyelwe ngokuqondile, izimo zokusabela zingathuthukiswa ngokushesha nangokunembile ngesikhathi esincane nokusetshenziswa kwezinto ezibonakalayo. kokubili isikhathi sokuhlala kanye nezinga lokushisa lokusabela kubhekwa njengemigomo eyimodeli ebalulekile.Ukusebenzisa isilungiseleli esakhelwe ngaphakathi sisebenzisa la magama akhethiwe kukhiqiza isethi yezimo zokusabela eziklanyelwe ukukhulisa izindawo eziphakeme kakhulu zomkhiqizo kuyilapho kunciphisa izindawo zokuqala eziphakeme kakhulu.Lokhu kulungiselelwa kuveze ukuguqulwa okungu-53% komkhiqizo we-triazole, okufana eduze nesibikezelo semodeli esingu-54%.
Ngokusekelwe ezincwadini ezibonisa ukuthi i-copper(I) oxide (Cu2O) ingasebenza njengezinhlobo ezisebenzayo ze-catalytic ezindaweni zethusi eziyiziro-valent kulokhu kusabela, ikhono lokukhipha i-oxidize indawo ephendulayo ngaphambi kokwenza ukugeleza kokugeleza kwaphenywa70,71.Ukusabela phakathi kwe-phenylacetylene ne-iodoethane kwase kwenziwa futhi lokhu kuqhathaniswa nezimo eziphawulekayo futhi kwaba nomphumela ophawulekayo wokuthi ukulungiswa kwaphinde kwaqhathaniswa kwaphinde kwabonwa ngaphansi kwezimo ezinhle. ekuguqulweni kwento yokuqala, eyabalwa ukuze> 99%.Nokho, ukuqapha kwe-HPLC kubonise ukuthi lokhu kuguqulwa kunciphise kakhulu isikhathi sokusabela esinde ngokweqile kuze kube yimizuzu engaba ngu-90, lapho umsebenzi ubonakala uhlehla futhi ufinyelela "isimo esizinzile". izinga lokushisa ukuze kwakhiwe i-CuO ne-Cu2O okungezona izingqimba zokuzivikela.Lokhu kuqeda isidingo sokwengeza umthombo wethusi osizayo(II) wokuhlanganisa ndawonye71.